Process for producing fast dyeings on polyamide fiber material



United States Patent A PROCESS FOR PRODUCING FAST DYEINGS ON The present invention concerns a process to attain fast dyeings on polyamide material as well as the polyamide material fast dyed by this process.

It is well known to be unavoidable in dyeing with fiberreactive dyes that a certain amount of the dyestuff is saponified during reaction with the fiber molecules. A portion of this saponified dyestuff product remains on the dyed fibers even after the dyeing process itself, including 'the known fixation treatment, has been terminated. It is,

therefore, necessary to remove this residual saponified product as completely as possible from the dyed fibers, since otherwise the fastness properties of the dyed material leave much to be desired. This removal has hitherto been effected by an alkaline after-treatment, which, however, leads to ,a deterioration of the mechanical properties of polyamide fibers, and particularly of wool. Moreover, the removal of the saponified dyestulf product by the saidafter-treatment is more or less incomplete, depending on the nature of the dyestuff used, thereby rendering it difficult or impossible to attain optimal fastness properties in the dyed polyamide fiber materials.

It is therefore ,an object of the present invention to provide a process for producing fast, fiber-reacted dyeings on polyamide fiber materials, as Well as fiber-reactive dyes suitable for use in the new process, whereby it becomes possible to remove practically completely the portion of saponified dyestuff product remaining on the fibers after the dyeing step proper, and thus to obtain dyed material of optimal fastness properties being substantially free from deterioration of its mechanical properties due to after-treatment.

It is another object of the present invention to provide a process for producing fast fiber-reacted dyeings on polyamide fibers wherein .alk'aline after-treatment of the dyed polyamide fibers is avoided.

It is yet another object of the invention to provide novel dyestuffs suitable for use in the production of fast fiberreacted dyeings on polyamide fiber materials, which permit after-treatment for the removal of saponified dyestuff product residual on the fibers after the dyeing step proper without the use of alkaline media.

It is a further object of the invention to provide processes for the dyeing of wool on the one hand and silk and nylon-type fibers on the other hand, with reactive dyes which lead to dyeings with good all round fastness properties in satisfactory yields, and the saponification products of which occurring during dyeing can be removed by lafter-treatment which does not affect the mechanical properties of the dyed fibers unduly.

It is still a further object of, the invention to provide dyeings of polyamide fiber-mate1ials with fiber-reactive dyes of the above characteristics which dyeings possess good allround properties and the mechanical properties of which are substantially unimparied by the after-treatment according to the above-mentioned process according to the invention.

These objects are attained in accordance with the present invention by a process for the production of fast fiberreacted dyeings on polyamide fiber materials, which process comprises:

(a) Dyeing the aforesaid material initially at a temperature below C. from a long bath having a pH in the range of from 5 to 11 depending on the nature of the polyamide material, which bath consists essentially of an aqueous solution of an effectively coloring amount of a cationic reactive dyestuff bearing in its molecule: (i) from one to two fiber-reactive groupings each of which is linked to the per se non-reactive dyestuff structure of said dyestuff via a member selected from the group consisting of a carbon atom being an integral part of said per se nonreactive structure, the group NH, the group (ii) from one to two positive electrical changes, per molecule, which are stable during dyeing and each of which is localized at an atomic entity outside any fivemembered heterocyclic aromatic ring of said dyestuff and being separated by at least two carbon atoms from the nearest fiber-reactive grouping, and imparting cationic character to said dyestuff, and raising the temperature in the bath to a range of from 80 C. to the boiling point of the bath, While maintaining the pH of'the bath in a range of, in the case of 'wool about 5 to 8, and, in the case of silk and nylon-type fiber material, about 5 to 11, the goodsto-liquor ratio being preferably from 1:60 to 1:20;

(b) Raising the temperature of the said bath to above 80 C. thereby fixing the reactive portion of the said dyestuff on to the fiber material, and

(c) Extracting colored saponified dyestuff product produced from said cationic reactive dyestuff during the preceding phases of the process, from the dyed material by subjecting the latter to a treatment in an aqueous weakly acid solution of a lower alkanoic acid, which solution has a pH of about 3 to 5.5, either by altering the pH of the aforesaid long bath by adding an adequate amount of organic acid, preferably formic or acetic acid, or by transferring the goods from the aforesaid bath to an aqueous extracting bath of a pH in the last-mentioned range, containing preferably formic acid or acetic acid as acidifying agent.

The above-defined fiber-reactive dyestuffs usable in the process according to the invention are characterized by the presence, under the conditions prevailing during the above steps (a) and (b) of the said process, of a cationic charge which is retained in the dystuffs even after an eventual saponification of the fiber-reactive grouping and after the bond between dyestuff and fiber molecules has been effected. It is particularly characteristic of the dyestuffs defined above that proportions of saponified products derived from them can be removed easily under mild conditions, i.e. in an organic acid aqueous medium, in particular of acetic acid or formic acid, in a pH range as defined under step (c) supra, thereby preserving the mechanical properties of the fibers practically unimpaired, 1

while greatly enhancing the wet fastness and related fastness properties of the resulting dyeings on polyamide fibers.

The dyestuffs used according to the invention can be of the most various classes. They are preferably of the technically proved classes of dyestuffs, the azo anthraquinone, phthalocyanine, nitro or formazane dyestuffs and they may also contain metals such as copper, nickel, chromium or cobalt. Of the azo dyestuffs, mainly monoazo dyestuffs are used, eag. those of the type benzene-azohydroxybenzene, benzene-azo-aminobenzene, benzene-azohydroxynaphthalene, benzene-azo-aminonaphthalene, benzene-azo-hydroxypyrazole, benzene-azo-aminopyrazole, benzene-azo-acyloacetylarylamide or those of the analogous naphthalene-azo and heterocycle-azo types, whereby 5- or 6- membered heterocycles are meant, particularly those containing nitrogen such as thiazoles, imidazoles, triazoles, tetrazoles, oxdiazoles, thiadiazoles, pyridines, pyrimidines, benzthiazoles, benzimidazoles, benztriazoles, indazoles, quinolines. Polyazo dyestuffs, however, can also be used.

Of the anthraquinone dyestuffs, preferably derivatives of amino or diamino anthraquinone are meant the amino group of which (which is preferably substituted) is, in particular, in the tat-position.

Particularly suitable for use in the dyeing process according to the invention are those of the above-defined novel cationic reactive dyestuffs in which the non-reactive structure is that of an unmetallized azo or an anthraquinone dyestuff radical as defined above.

The cationic character of the dyestuffs used according to the invention is due to the presence of positively charged substituents, the number of which in the dyestufl molecule must always be greater than the number of anyacid groups present such as sulfonic acid or carboxylic acid groups. As positively charged substituents, these dyestuffs contain, for example, amino, particularly tertiary amino groups, quaternary ammonium, phosphino and quaternary phosphonium or sulfonium groups, also hydrazinium, thiuronium, guanidinium or amidinium groups. The cationic nature of dystuffs used according to the invention can also be derived from metal bound in complex linkage such as in chromium or cobalt containing o,o-dihydroxyor o-hydroXy-o'-amino azo dystuffs of the type 1 dyestuff moleculezl metal atom. However, the drawing power and/ or solubility of these dyestuffs often leaves to be desired.

The preferred substituents having a positive charge are tertiary amino groups as well as quaternary ammonium groups. As N-substituents, these contain aliphatic, cycloaliphatic or araliphatic groups; the N-substituents can also form non-aromatic rings having 5 to 8 members, particularly 6 members. Low alkyl groups each having 1 to 4 carbon atoms are the preferred N-substituents.

In particular the following atomic entities, Q, at which the position charge is localized as indicated below, are recommended in dyestuffs usable according to the invention:

C 11 Q Ag -02m Q -Ne Q14 PCH Of the above atomic entities Q to Q and Q to Q inclusive, fall under the preferred generic formulas wherein 1'1 I P-lower alkyl lower alkyl wherein r has the above meaning; and

lower alkyl lower alkyl The dyestuffs used according to the invention contain the groups usual in anionic reactive dystufis as fiberreactive groups. The reactivity of these groups is due either to a polylinkage which is capable of addition or to a substituent which can be split olf as tertiary amine or as anion. For example they contain the grouping as polylinkage capable of addition such as the acrylyl, methacrylyl, a-chloroor a-bromo-acrylyl group, or the grouping COCEC-, e.g. the radical of propiolic acid, or the grouping such as, e.g. the vinyl sulfonyl group, or also the isocyanate or isothiocyanate group.

Other dyestuffs usable according to the invention are those containing a quaternized tertiary reactive amino substituent which is split off under the dyeing conditions according to the invention, thereby establishing linkage between the resulting dyestuif radical and the fiber molecule. Such fiber-reactive cationic groupings are, for instance, the pyridinium, trimethylammonium and other quaternary ammonium derivatives of similar structure, for instance 1,4-diazabicyclo[2,2,2]octane-(l) radical, which can be split 0E as tertiary .amines.

As preferred fiber-reactive groups however, the dyestuffs used according to the invention contain substituents having a radical which can be split 01f as anion, preferably mobile chlorine or bromine and, sometimes,

the OSO R- group wherein R is hydrogen, or a metal. The mobility of such radicals which can be split off as anion is due, for example, to the influence of electrophilic groups such as the -C0 or SO,; group in saturated aliphatic radicals. Examples of such radicals are those of aliphatic chlorocarboxylic or bromo-carboxylic acids, e.g. the radical of chlor-oor bromo-acetic acid, fl-chloroor fi-bromo-propionic acid, fi-chloroor fi-bromo-acrylic acid, a,p-dichloroor a, 3-dibromo-acrylic acid, aor fi-chloro, or aor /8-bromo-crotonic acid or 0a,}3-di6h10l'OCIOtOBiC acid. Or the mobility of the halogen atom of such radicals is due, in the case of aromatic radicals, to the influence of electrophilic groups in oand p-positions, e.g. nitro, hydrocarbon sulfonyl or hydrocarbon carbonyl groups, or their mobility is due to the bond to a carbon atom in the ring adjacent to a tertiary ring nitrogen atom such as in chloroor bromo-s-triazinyl or chloroor bromo-pyrimidyl radicals. For facility of production and economy reasons, preferred fiber-reactive groups are the radicals of saturated halogen fatty acids, in particular the radical of chloroacetic acid.

The following fiber-reactive groupings, Z, are especially preferred in the dyestuffs usable according to the invention:

Both the cationic substituents as well as the fiberreactive substituents can either be bound direct or by Way of bridging members to the actual dyestuif structure. Also one of these substituents can be a substituent of the other. In the latter case, either the cationic substituent is bound by. way of the fiber-reactive substituents to the dyestuft as, for example, when the fiber-reactive group is a monochloroor monobromo-s-triazinyl radical which contains as substituent a cationic group such as an w-quaternary ammoniumethylamino or ammonium propyl, or a por m-(quaternary ammonium)phenylamino group, the quaternized nitrogen of which groups is the atomic entity at which the positive charge determining the cationic nature of the dyestuff is localized. Substituents of the quaternized nitrogen atom are from two or three lower alkyl groups. However, the reactive nature of the fiber-reactive grouping must not vbe due to the presence of the cationic substituent and the latter must be present even after dyeing. Vice versa, the fiber-reactive substituent can be a component of the cationic group in that, for example, in a quaternary ammonium group at least one N-substituent contains a fiber-reactive radical, 'e.g. the chloroacetyl radical.

The following groupings combining Z and Q in one and the same substituent are particularly preferred in dyestuffs of this type usable according to the invention.

CH 6) R N OHZCONHCH2CH2NHG O CHzCl CH3 a; R -NCHzC ONHCHzOHzCHzNHCOOHzCl Ha)s N R all In addition the cationic and fiber-reactive substituents, the dyestuffs used according to the invention can also contain other substituents, e.g. halogens such as fluorine, chlorine or bromine, alkyl and alkoxy groups having in particular 1 to 4 carbon atoms, hydroxy, nitro, sulfonic acid, carboxylic acid, sulfonic acid amide and carboxylic acid amide groups, including N-substituted sulfonic acid aryl ester, carboxylic acid ester, acylamino, acyloxy groups, etc.

Dyestuffs usable according to the invention are obtained, for example, by reacting a dyestuff which contains at least one of the two critical groups, with a compound which introduces the other group. The reaction partners are preferably linked together by condensation with the formation of acid amide, acid ester or urea linkages.

Dyestuffs usable according to the invention which contain a quaternary onium group as cationic substituent are obtained by reacting dyestuffs which contain at least one group quarternizable with a quaternizing agent. In this reaction, one reaction partner must contain a fiberreactive group. As quaternizable groups, such dyestuffs contain chiefly a tertiary amino group, particularly a dialkylamino group having preferably 1 to 4 carbon atoms per alkyl radical, but they can also contain a tertiary phosphino or a thioether group.

The dyestuffs usable according to the invention can also be produced by forming them from dyestuff components which together contain at least one fiber reactive and one cationic group. This is the main method for producing azo, in particular monoazo, dyestuffs. Thus azo dyestuffs are formed by coupling a diazo component with a coupling component which together each contain at least one of the critical groups mentioned. This process is also suitable for the production of formazane dyestuffs.

The dyestuffs usable according to the invention must in all cases be produced under mild conditions, i.e. the reactions must be performed at the lowest admissable temperatures and at pH values which are as weakly alkaline as possible. This rule also applies to drying the dyestuffs. The dyestuffs obtained can be reduced in strength.

The polyarnide material is dyed in a weakly acid, neutral to weakly alkaline bath; wool preferably at a pH of 6.5 to 7.7, silk and nylon between pH 6 and 10. The pH required of the liquor is adjusted or maintained by the addition of the usual agents influencing the pH value. Such agents are, for example, weak acids such as acetic acid, or salts having an acid reaction such as ammonium sulfate, or weak bases such as hexamethylene tetramine,

or salts having a basic reaction such as alkali acetates, citrates, carbonates, bicarbonates and phosphates. Advantageously buffer mixtures are used as agents influencing the pH, for example, mixtures of primary and secondary alkali phosphates, ammonium acetate or a mixture of sodium acetate and acetic acid. In addition, the bath can contain the auxiliaries usual in the textile industry, for example, neutral salts such as sodium sulfate or ammonium acetate, or wetting or dispersing agents, e.g. non-ionogenic agents such as polyglycol ethers of higher fatty alcohols or polycondensation products of higher fatty acids with ethylene oxide, or cationic wetting, dispersing or retarding agents such as cetyl' trimethyl ammonium chloride.

The dyeing is begun advantageously at a bath temperature of about 40 C., the temperature is then raised and dyeing is performed for 15 to 60 minutes, preferably about 30 minutes at a temperature of about 80 to 100 C., preferably at about 100 C.

On using dyestuffs with a markedly high affinity to the fiber, too quick drawing of the dyestuffs onto the fibers can be prevented, for example, by beginning the dyeing under a pH of 5 and gradually raising the pH of the dyebath.

The dyestuff is fixed completely at about 80 to 100 C., preferably at 100 C. and extraction step (b) is carried out at a pH of about 3 to 5.5 preferably at about 3.5 to 5. The pH value is lowered advantageously by the addition, of sufficient amounts, preferably about 1% to 5% calculated on the weight of the goods being dyed, of formic acid or acetic acidto the extraction bath which may be the bath used for dyeing or another bath. Wool dyeings are advantageously finished in formic acid solution. If, in the previous dyeing, large amounts of basic buffer substances had been used, corresponding-1y larger concentrations of organic acid are necessary for the extraction treatment of the dyeing in order to attain the desired pH of 3 to 5.5. In this case, part of the excess of basic substances can also be neutralized by the addition first of an inorganic acid such as hydrochloric acid or sulfuric acid or of alkali metal bisulfate util a pH in the vicinity of 6 to 7 has been attained, formic or acetic acid then being used for the final adjustment of the pH. The wool dyeings obtained are after-treated either in the original dyebath or in a separate after-treatment bath, whilst silk and nylon are advantageously after-treated in a separate after-treatment bath.

The dyed and finished goods are advantageously rinsed and then dried.

The dyeing process according tothe invention is distinguished by the rapidity of the drawing and fixing of the dyestuffs and the large amount of dyestuff which is fixed, i.e. a high yield of dyestuif. Also, the mechanical properties of wool material are better preserved by the after-treatment with organic acids according to the invention than by the usual alkaline after-treatment. In addition, the process according to the invention is very well suited for shading. On wool, the process produces very level dyeings and there is no tendency to produce a skittery aspect of the dyeing. Mixtures of fibers of varying diameter are also dyed level. There is hardly any tendency to produce the undesirable stripey dyeings often occurring with nylon dyed by known processes.

Compared with dyeings obtained under hitherto known conditions with known dyestuffs of similar constitution, the dyeings obtained and finished by the process described above on polyamide materials, in particular on wool, have improved fastness properties to milling, hot water, sea water, perspiration and Washing.

The dyeing process according to the invention is also useful for dyeing blended fabrics consisting in particular of polyamide fibers, especially wool, with polyacrylonitrile fibers (union dyeing), (a) with one and the same dyestuff, or (b) with a mixture of (a) a cationic reactive dyestuff 13 according to the invention and (p) a conventional cationic polyacrylonitrile dyestutf.

In the latter case, it is a special advantage that the two dyestuffs are fully compatible with each other. In the past, such dyeing was usually carried out with mixtures of cationic dyestuifs having afiinity for the polyacrylonitrile type fibers and anionic wool dyestuffs, the lack of compatibility of which dyestuifs led to undesirable precipitations in the dyebath during dyeing.

Dyestuffs which contain a cationic charge localized at an atom of an aromatic, particularly of an aromatic fivemembered heterocyclic ring generally afford dyeings of iniq fast e a tqaarfi sma h dyeing? Often lack light fastness.

Further details of the invention will be seen from the following non-limitative examples. The temperatures are given therein in degrees centigrade. Percentages are given by'weight unless stated otherwise; g. stands for gram and ml. for .milliliter.

, Exarrvple 1 10 g. of worsted yarn are inserted in 400 ml. of a dye liquor having a temperature of 40 and containing 0.1 g. of the dyestutfhaving the formula W and ml. o f a solution of 9.6 g. Na' HPO -2H O and i 1.73 g. KH PO per liter. The dye bath is heated to boiling temperature and maintained at this temperature for to 1 hour.

The dyed material is then removed from the aforesaid dyebath and boiled for to minutes in 400 ml. of another aqueous bath: of 400.-ml. containing 0.4 g. of %-acetic acid. The material is then withdrawn from the bath, rinsed and dried. A blue dyeing is obtained which'has'good wet fastness.

The dyestuff described is produced as follows: 1 mol of l-chloro-ant'hraquinone in butanol, i siheated together with an excess .of 2 to 3 mols of l-(N,N-dimethylamino)- 3-arnino-propane to boiling until the reaction is complete. The resulting red product is separated and then reacted with 1 mol of bromine in glacial acetic acid. The t-bromo- 1-(dimethylam'inopropylamin-o)-anthraquinone obtained is purified by recrystallization and then heated in an excess of l,3-diaminopropane the mixture turning blue. After completion of the reaction the excess of 1,3-diaminopropane is removed by distillation. '1 mol of the 4-[3'-aminopropylamino]-1-[3'-dimethylaminopropylamino] anthraquinone is dissolved inwater together with an, equivalent amount of hydrochloric acid and reacted in a mixture of water/acetone/sodium acetate (weight ratio 10:10: 1) with 1.2 mols of chloroacetyl chloride. The resulting blue dyestuff is salted out with sodium chloride, separated by filtration and dried in vacuo.

Example 2 10 g. nylon fabric are introduced into 400 ml. of a dye liquor having a temperature of 40 and containing 0.1 g. of the dyestuif of the formula and 0.3 g. of crystallized trisodiumphosphate. The bath is is quaternized with dimethylsulfate. The 4-[3'-chloroacetylamino phenylamino] 1-[3"-t1imethylammoniurn-propylamino]-anthraquinone chloride is saponified by boiling a with aqueous 2 N-hydrochloric acid and the saponification product is then chloroacetylated with chloroacetic acid chloride. I

Example 3 10 g. of worsted yarn are introduced into 400 ml. of a dye liquor having a temperature of 40 and containing 0.1 g. of the dyestufl" of the formula and 10 ml. of a solution of 9.6 g. of Na HPO -2H O and "1.73 g. of KH PO per liter. The dye bath is heated to boiling temperature and maintained at this temperature for one hour. v

The pH of the dyebath which still contains the goods is then adjusted to 3 by the addition of aqueous 85%- formic acid and the dyed material is boiled in the same bath for another 15 minutes. The material is then rinsed and dried. A red dyeing is obtained which has good fastness to wet processing.

The above dyestulf is produced by quaternizing 1 mol of 1 [N,N dimethylarninopropylamino]-anthraquinone produced as described in Example 1 from l-chloro-anthraquinone and an excess of 1-[N,N-dimethylamino] -3-amino-propane, with 1.6 mols of 1,2 bis [N chloroacetylaminoJ-ethane in acetonitrile. 4

In a similar manner as described in Examples 1 to 3, the dystuifs falling under the formula f 0 f l i 12 Y Y it (i n the substituents of which are defined in Table I below, are produced from the correspondingly substituted starting materials by the method of the example given in the last column of the aforesaid table.

27 Example 51 (a) g. of wool flannel are introduced at 40 into 400 m1. of a liquor which contains 0.1 g. of the dyestufi of the formula and 0.3 g. of ammonium acetate. The bath is brought to the boil within 30 minutes and kept for 30 minutes to 1 hour at this temperature. 0.3 g. of 85% formic acid are then added and the bath is again boiled for l530 minutes.

The dyed goods are rinsed and dried. An orange, very level wool dyeing having good fastness properties is obtained.

28 (b) The dyestuff mentioned is obtained by coupling diazotized 3 (chloroacetylamino) aniline with 1-(4'- trimethylammonium acetylaminophenyl) 3 methyl- 5 pyrazolone (as chloride).

(b) The dyestuif mentioned is obtained by coupling within 24 hours and is isolated in the form of the chloride.

To produce the coupling component, N-methyl-N-phenylpropylenediamine, with the addition of 2 mols of sodium acetate, is reacted at room temperature with 2 mols of chloroacetyl chloride in a mixture, (volume ratio 1:1) of acetone and water, and the reaction product is separated as an oil by diluting with water and adding sodium hydroxide solution until the pH is 7. The oil is washed with water, taken up in ether, again washed twice with water and then the ether is distilled off.

Example 52 (a) 10 g. of wool slubbing are introduced into 400 m1. of a 60 warm liquor which contains 0.15 g. of the dyestuff of the formula l Nnooomol 10 ml. of a solution of 9.6 g. of Na HPO .2H O and 1.73 I g. of KH2PO4 per liter. The dyebath is brought to the" acid. The goods are then rinsed and dried. A yelloWf.

colored wool is obtained which has very good-wet fastness properties.

The coupling component can be produced from 1-(4- chloroacetylaminophenyl) 3 methyl 5 pyrazolone and trimethylamine in dimethyl formamide at room temperature within 15 hours. It is in the form of its chloride.

Example 53 10 g. of wool are introduced into 400 ml. of a dye liquor having a temperature of 60 and containing 0.15 g. of the dyestuff of the formula as well as 10 ml. of a solution of 9.6 g. of Na HPO -2H O and 1.73 g. of KI-I PO per liter. The dye bath is then heated to and maintained at this temperature for one hour. The dyed material is then removed from this bath and boiled in 400 ml. of another aqueous bath containing 0.4 g. of aqueous 40%-acetic acid. Thereafter, the material is rinsed and dried. An orange dyeing is obtained which has good fastness to wet processing.

The above dyestufi is obtained. by the diazonium salt of coupling aniline-3 -carboXylic-acid( 3'-N,N-dimethylamino) propyl-amide with 2-hydroxynaphthalene and quaternizing the resulting dyestuff in acetonitrile as solvent with an excess of 1-chloroacetyl-4-chloroacetylamino benzene.

Example 54 NHCOCHzOI and 0.8 g. of sodium carbonatefi The bath is brought to the boil within 30 minutes and boiled for 30 minutes to 1 hour.

The dyed goods are boiled for 15-30 minutes in 400 ml. of a fresh bath containing 0.3 g. of 85% formic acid and then rinsed and dried. The yellow silk dyeing obtained has good wet fastness properties.

The dyestuff of the above constitution is obtained by coupling diazotized w-trimethylammonium-4-aminoacetophenone (as chloride) with 1-(4'-chloroacetylaminophenyl)-3-methyl-5-aminopyrazole.

The coupling component is obtained by dissolving l-'(4 aminophenyl)-3-methyl-5-aminopyrazole in 60% dioxan, adding 2 mols of sodium acetate and 1.1 mols of chloroacetyl chloride to the solution and stirring the reaction components for 1 hour at 35. The solution obtained can be used direct for the coupling.

Example 55 10 g. of nylon staple fiber are introduced into 400 ml. of a 40 warm bath which contains 0.1 g. of the dyestulf given in Example 1 and 0.3 g. of crystallized trisodium phosphate. The bath is then heated to 100 and keptat this temperature for 30 minutes to 1 hour. 1.4 g. of 85% formic acid are then added to the bath which is then boiled for another 15-30 minutes. The dyed goods are rinsed and dried.

An orange nylon dyeing which has very good wet fastness properties is obtained. An equally good dyeing is obtained if the dyed goods are after-treated in a fresh bath with formic acid analogously to Example 2.

Example 56 10 g. of previously wetted wool flannel are introduced into 400 ml. of a 40 warm liquor which contains 0.1 g. of the dyestuff given in Example 1 and 0.1 g. of the dyestuff given in Example 3. The bathis heated to 100, 10 ccm. of a buffer solution containing 9.6 g. of

and 1.73 g. of KH PO per liter are added within 15 minutes and the bath is boiled for a further 15 to 45 minutes. 0.5 g. of 85% formic acid are then added to the liquor which is again boiled for 15-30 minutes. The dyed goods are rinsed and dried.

A very level orange-yellow wool dyeing is obtained which has good fastness properties.

The dyestuffs given in the following Tables II-V can also be used by the methods described in Examples 51 to 56 and level dyeings which have good wet fastness properties are also obtained.

In a similarmanner as described in sections (b) of Examples 51 to 5 6, the dyestuffs falling under the formula the substituents of this fundamental benzene-azo-p-aminobenzene skeleton of which are defined in Table II below, are produced from the diazonium compounds and coupling components substituted as indicated in the said table.

Also in an analogous manner as described in section (b) of Examples 51 to 56, supra, the dyestuffs falling under the formula b2 b1 bu io l b b b i the substituents of the fundamental brizene-azo-naphthalene skeleton of which are defined in Table IV below, are produced from the corresponding substituted diazonium compounds and coupling components. Fast dyeings on wool are obtained with these dyestuffs in the shades given in the last column of Table IVbelow, in accordance with the dyeing procedure given in Example 51 (a) Also in an analogous manner as described in section (b) of Examples 51 to 56, supra, the dyestuffs falling under formula the substituents of the fundamental benzene-azo-pyrazom I I I 3 IN II I II I III II I I I I I II II I: 2 I I II I I I I II t2; N N m N m N m II I II II- I Is II II I III I IAIH III II Z I I III 333 II NII- I III- II I I I I I II II 333 II N II I III II I I I I I II II I I II N II I IIT II I I I II IIs I II I I N i m I -N II I: .II I II III II I I I I III I II 2 I I II NII- I III- II I I I I I II II 333 WII III- wII I IIT II I I I I I II .0 I N II 333 II I II III II I I I I II IIIIII III II I320 N N m N II 3 II N II I III II I I I @I a- II 62 BQIISQ SI 9:383 .875 x w w I m m m n 02 532 03 I I I I m N I I I I I; II 5 III II II II- II I I II II- I I I2 2 .7 I IIEI I N N N n ..N I. II I: .5 I II II II II II I I I II II I IIIEI I N N N I I II I: .5 III II II II II I II I I I I I-II"II- II 55.. a NII II II- II I I I I III II- I II -.I: III I I II v .7 I953 N N I mN m N A. I. II I: .5 I II II II I I I III I II I. I IIIEI I- N, N i @N H .4 N I. II I: .5 I II II II I I I I I II I, I II III? a 2 -II- I III- II I v I I--IIIIII I I I s I-II- I II II I II I I II is: N I II I I I I I I: .I II III II I I I IIIII I I $293 I. .I I N ..MN I .Y I. n N II I2 IIII I III II I I I I II III 62 22.5 2 I. p I I. H. I I I I EBSI 5.3% .I I3 I x I. m m n m NI 

1. A PROCESS FOR THE PRODUCTION OF A FAST, FIBER-REACTED DYEING ON POLYAMIDE FIBER MATERIAL, COMPRISING: (A) DYEING THE AFORESAID MATERIAL INITALLY AT A TEMPERATURE BELOW 80*C. FROM A LONG BATH HAVING A PH IN THE RANGE OF FROM 5 TO 11 DEPENDING ON THE NATURE OF THE POLYAMIDE MATERIAL, WHICH BATH CONSISTS ESSENTIALLY OF AN AQUEOUS SOLUTION OF AN EFFECTIVELY COLORING AMOUNT OF A CATIONIC REACTIVE DYESTUFF BEARING IN ITS MOLECULE (I) FROM ONE TO TWO FIBER-REACTIVE GROUPINGS EACH OF WHICH IS LINKED TO THE PER SE NON-REACTIVE DYESTUFF STRUCTURE OF SAID DYESTUFF VIA A MEMBER SELECTED FROM THE GROUP CONSISTING OF A CARBON ATOM BEING AN INTEGRAL PART OF SAID PER SE NONREACTIVE STRUCTURE, THE GROUP -NH-, AND THE GROUP 